Painting composition

ABSTRACT

A PAINTING COMPOSITIONS CONTAINING A CHLORINE-CONTAINING POLYMER SELECTED FROM THE GROUP CONSISTING OF CHLORINATED RUBBER AND CHLORINE-CONTAINING SYNTHETIC RESIN, AND AT LEAST ONE OF COMPOUNDS REPRESENTED BY THE FORMULA (I):   AR1-R-AR2-R-AR3   WHEREIN R IS ALKYLENE SELECTED FROM THE GROUP CONSISTING OF   -CH(-CH3)- AND -C(-CH3)2-   AND ANY ONE OF AR1, AR2, AND AR3 IS ALKYLPHENYL (AR1 OR AR3) OR ALKYLPHENYLENE (AR2), SAID ALKYL HAVING 1-3 CARBON ATOMS, THE NUMBER OF ALKYL RADICALS BEING 1-3, ANRD THE NUMBER OF CARBON ATOMS CONTAINED IN ALL OF THE ALKYLS BEING 1-3, ALTERNATELY ANY TWO OF AR1, AR2, AND AR3 ARE PHENYL OR TOLYL (AR1 AND/OR AR3), OR PHENYLENE OR METHYLPHENYLENE (AR2).

United States Patent 3,833,680 PADITING COMPOSITION Michiaki Tor-ii,Tokyo, Japan, assignor to Nippon Petrochemicals Company, Limited, Tokyo,Japan No Drawing. Filed Mar. 26, 1973, Ser. No. 344,772 Claims priority,application Japan, Mar. 27, 1972,

Int. Cl. C08c 11/22, 13/04 US. Cl. 260-735 6 Claims ABSTRACT OF THEDISCLOSURE A painting composition containing a chlorine-containingpolymer selected from the group consisting of chlorinated rubber andchlorine-containing synthetic resin, and at least one of compoundsrepresented by the formula (=1):

AI1RA12RAI3 wherein R is alkylene selected from the group consisting ofand any one of Ar Ar and Ar is alkylphenyl (Ar, or Ar or alkylphenylene(Ar said alkyl having l-3 carbon atoms, the number of alkyl radicalsbeing l-3, and the number of carbon atoms contained in all of the alkylsbeing l-3, alternatively any two of Ar,, Ar and Ar;, are phenyl or tolyl(Ar, and/or Ar or phenylene or methylphenylene (Ar- BACKGROUND OF THEINVENTION 1. Field of the Invention Paints obtained from chlorinatedrubber or chlorinecontaining synthetic resin are generally used in thebottom, exterior, deck and superstructure of a ship as anticorrosivepaints and particularly as paints for ships placed under the severecorrosive action. Moreover, paints using chlorinated rubber system orthose using chlorine-containing synthetic resin system such aschlorinated polyethylene, polyvinyl chloride system, or vinyl chloridecopolymer have long been used as paints for retaining water andchemicals resistances so as to obtain good results in painting not onlyships but also structures on land. Further, these paints more easilyform a thick layer than the vinyl resin type paint, and, even if paintedrepeatedly on the previously painted surface after drying, the solventand vehicle contained therein more increase the adhesion of the oldlayer to the new layer. Thus, these paints are most appropriate also forcoating in a .repair work wherein an extremely quick drying character isrequired.

Chlorinated rubber type or chlorine-containing synthetic resin typepaints have been manufactured heretofore by various processes. Thesepaints are broadly divided into paints of pure type formed by combiningchlorinated rubber or chlorine-containing synthetic resin withplasticizer and those of blend type using other synthetic resin such asalkyd resin and various varnishes together with the above combination.If only chlorinated rubber or chlorine-containing synthetic resin basesare employed, the painted layer is hard to be formed and cracks easilytake place in the layer. To prevent such disadvantages, it is necessaryto use a considerable amount of plasticizer.

As plasticizers, chlorine compound type plasticizers such aspolychlorinated biphenyl (PCB), chlorinated parafiin and triphenylchloride have been generally used heretofore.

Such chlorine compounds, however, are toxic ones which are taken intoand accumulated in the human body to cause various evils. In addition,these compounds are very harmful to human life as environment-pollutingmaterials because they are highly stable and difficult to decompose. Asa result of using a large quantity of plasticizer such as PCB foranticorrosive paints of ships, much plasticizer flows into sea-Waterthereby causing problems of environmental pollution.

Accordingly, there has been demanded as a chlorinated rubber andchlorine-containing synthetic resin type paint a painting compositionwhich contains a harmless stabilizer having good compatibility with thepainting base as Well as excellent water and chemicals resistances anddurability. For that purpose, various plasticizers for paints including,for example, phthalate ester type or phosphate ester type or ester ofaliphatic acid have been studied, but these plasticizers have variousdrawbacks such as poor Water resistance and difficulty in obtaining asatisfactory layer.

SUMMARY OF THE INVENTION DESCRIPTION OF THE INVENTION The paintingcomposition of this invention contains chlorinated rubber orchlorine-containing synthetic resin, and, as a plasticizer, one or moreof compounds represented by the following formula (I):

and any one of Ar,, Ar and Ar;, is alkylphenyl (Ar Ar or alkylphenylene(AT2), said alkyl having 1-3 carbon atoms, the number of alkyl radicalsbeing l-3, and the number of carbon atoms contained in all of the alkylsbeing l3, alternatively any two of Ar Ar;, and Ar are phenyl or tolyl(Ar Ar or phenylene or methylphenylene (Ar The process for producing thecompound represented by the formula (I) may include a method forreacting a lower alkylbenzene selected from the group consisting oftoluene, ethyl benzene, xylene, methylethyl benzene, trimethyl benzene,isopropyl benzene, n-propyl benzene and mixtures thereof withphenylmethyl carbinols, a method by Friedel-Crafts reaction and, moredesirably, a method for reacting styrene or a-methyl styrene with theabove lower alkyl benzene by using sulfuric acid catalyst. If, forexample, xylene reacts with styrene by using sulfuric acid catalyst, itis inferable by gas chromatography, NMR and ether means that thecompounds represented by'the following formulae (II)-(IV) together withother isomers can be obtained:

CH: CH:

H H t'@ CH3 (II) CH3 CH3 H E Q 3H3 CH3 (IV) From ortho-xylene andstyrene, there can be obtained a mixture of the compounds (H) and (III),and the ratio of (II) to (H1) varying depending upon the condition ofproduction. From meta-xylene and styrene, the compound (IV) can beobtained. From mixed xylene, a mixture of (II), (III) and (IV) can beobtained.

The compound represented by the formula (I) can be obtained by variousmethods and a mixture of isomers falling under the formula 1-) isobtainable as the method of production varies.

The compound of the formula (I) to be used for the object of thisinvention may be a single compound or a mixture.

The compound represented by the formula (I) makes an excellentplasticizer when used in chlorinated rubber or chlorine-containingsynthetic resin paint and particularly in anti-corrosive paint.

' Among the compounds represented by the formula (1), those indicated bythe formula (ID-(IV) are industrially easily preparable and showingexcellent painting properties. Of course, however, other compoundsindicated by the formula (I) also have good painting properties.

When using as a paint the painting composition of this invention, resinssuch as alkyd resin, cumarone-indene resins, petroleum resins, phenolicresins and rosin as well as solvents, pigments and others areappropriately added in order to improve workability, weatheringresistance and other properties according to the purpose and the placeof use. l-50 parts by weight of the compound represented by the formula(I) can be used as a plasticizer on the basis of 100 parts by weight ofchlorinated rubber and/or chlorine-containing synthetic 'resin.

The increase in the amount of plasticizer lowers water and chemicalsresistances which constitute characteristic features of the base used.Moreover, if the plasticizer is small in quantity, properties of thepaint are also influenccd disadvantageously by cracks formed in thepainted layer. Typical chlorine-containing synthetic resin type paintbases include chlorinated polyolefin such as chlorinated polyethyleneand chlorinated polypropylene as well as polyvinyl chloride and vinylchloride copolymer.

DESCRIPTION OF PREFERRED EMBODIMENTS Example 1 A mixed xylene (o: 95%,m: 2%, p: 2% and ethylbenzene 1%) was reacted with styrene in thepresence of 95% H580 at a temperature of 510 C. Then, a fraction whichwas a mixture mainly composed of compounds represented by the aboveforrnulae (ID-(IV) and which had a boiling point within the range of 360390 C. (7 60 mm. Hg) was separated from this reaction mixture. Thefraction is referred to as Sample 1.

The fraction having a boiling point within the range of 192225 C. (at 2mm. Hg) which was obtained by ,4 replacing styrene with mixed vinyltoluene in the process for preparing Sample 1 is referred to as Sample2.

The C fraction obtained from the catalytic reformer of naphtha (thefraction is composed of 2.81% xylene, 1.17% isopropyl benzene, 4.37%n-propyl benzene, 31.12% metaand para-ethyl benzenes, 8.53% 1,3,5--trimethyl benzene, 7.36% ortho-ethyl toluene, 33.78% 1,2,4-trimethylbenzene, 7.68% 1,2,3-trimethyl benzene, and 3.21% other components) wasdiluted with steam and subjected to dehydrogenation reaction at 600 C.by using dehydrogenation catalyst Shell 105 (trademark of Shell) mainlycomposed of iron oxide. The resulting mixture containing (it-methylstyrene and vinyl toluenes) reacted as it was under the same conditionas that of Sample 1. The fraction separated from the resulting productand having a boiling point within the range of 193-231 C. (at 2 mm. Hg)is referred to as Sample 3.

Properties of the chlorinated rubber type painting compositioncontaining these three Samples 13 were compared with those of the priorchlorinated rubber system painting composition containing PCB,chlorinated parafiin, tricresyl phosphate (TCP), or butyl benzylphthalate (BBP). The composition ratios of the products were shown inTable 1.

Tests for measuring properties of the product were mainly conductedaccording to 1 15 K5400 and 118 K- 5401. The test results were shown inTable 2. Data appearing in test items ranging from pencil hardness toacid resistance in the Table 2 are values obtained by measuringcomposition A while those appearing in test items ranging from speculargloss to weathering resistance are values obtained by measuringcomposition B. The characteristics of the painting composition by thisinvention appearing in respective test items are as follows: (1) Pencilhardness (JIS K5401): The hardness of layer of the product by thisinvention was higher than that of the prior product using chlorinatedparafiin,

T CP, and BBP.

(2) Cross cut test (JIS K5400): The product by this invention wassuperior in adhesive property to the prior product using chlorinatedparaffin, TCP, and BBP.

(3) Water resistance (JIS K5400): When using the prior productcontaining chlorinated parafiin, TCP, and BBP, the surface of the metalwas rusted and the Water resistance being also poor. On the other hand,the product by this invention brought about neither rusting norswelling.

(4) Alkali resistance (IIS K5400): The product by this invention wasexcellent in alkali resistance similarly to the prior product usingchlorinated paraflin or TCP, while the prior product employing BBP waspoor in the resistance since BBP partially passed into the alkalisolution.

(5) Benzine resistance (JIS K-5400): The product by this invention Wassimilar to the prior product in this property.

(6) -.Acid resistance (IIlS K-5400): The product by this invention wasexcellent in this property similarly to the prior product.

(7) Specular gloss (JIS K-5400): After drying the product by thisinvention at normal temperature, the specular gloss on the mirrorsurface at an angle of 60 was measured. The specular gloss of thisproduct was 92.8% in reflection ratio, while that of the prior productgggained within the range of above and below (8) Adaptabilities forrepeated painting and for upper painting (JIS K-5400, respectively): Theproduct by this invention was more excellent than the prior product inthese properties.

(9) Weathering resistance (JIS K-5400): As a result of the acceleratedaging test conducted by using Weather- O-Meter (200 hrs; 60 C.), it wasfound that the product by this invention became less yellow than theproduct using chlorinated paraffin and TCP. Even after 200 hrs., thespecular gloss of this product was more excellent than that of theproduct using other plasticizer. The rate of decrease in the speculargloss of this product was lower than that of the prior product.

As is clear from the test results as stated above, it is found that theproduct by this invention is excellent not only in respective test itemsbut also on the whole evaluation. Same results were obtained also byusing chlorinated polyethylene as a chlorine-containing synthetic resininstead of chlorinated rubber.

(A) R is Ar and An; are each phenyl; and Ar is cresylene; and (B) R isAr; is phenyl; Ar is phenylene; and Ar is ortho cresyl.

TABLE 2.TE ST RESULTS Plasticizer Example Comparative example Product ofthis invention Chlorinated BBP Reference (Sample No.) parafiin TCP(Butylexample Test items (Pencil hardness: by JIS K5401, other items: byI IS (Tricresylbenzyl- K5400 2 3 70 phosphate) phthalate) P CB Pencilhardness on- The fourth day. 3B 3B 33 B HB 28 38 KB The tenth day HB HBB F F B B F Cross cut test spots; After 6 day 8 8 7 7 8 6 5 3 Tape test(rate of preservation percent) 100 99 98 98 98 96 95 10 0 Waterresistance:

3 days O O O O X A A A 6days O O O A X A A A Salt water resistance (byimmersing in 3% NaOl):

days O O O A X A A O 6 days O O O A X A A O Alkali resistance (5% NaOHda O O O O O O X A Benzine resistance (benzme 8, toluene 2); 5 hours- AA A X A X A O Acid resistance (20% H2804):

3 days O O O O O O O O 6 days O O O O O O O O Specular gloss; Reflectionratio at an angle of 60, percent- 92. 8 90. 3 88.0 86. 8 86. 2 81. 7 87.8 87 7 Adaptability for repeated painting (U Adaptability for upperpainting (1) (l) (l) Weathering resistance (Weather-O-Meter, 200 hrs.:60 0.):

Degree of becoming yellow 0. 0 0. 0 0.010 0.016 0. 016 0. 002 0 014Specular gloss (reflection ratio at an angle of 60) 8 84 82 82 68 62 8 21 Good.

NorE.O=satisfaetory: A=ordinary: X=inierior.

Example 2 The results obtained by the test for comparing the acutetoxicity of the plasticizer used in this invention with that of PCB(polydiphenyl chloride) are shown in Table 3. From this table, it isfound that the product by this invention is very low in toxic character.

Table 3 The product of this invention (1,2-bis-umethylbenzyl 4,5dimethylbenzene) PCB. LD (oral administration) Rat 10.19 g./kg. Mouse1.8 g./kg.

I claim:

1. A painting composition comprising chlorinated rubber and 10 to partsby weight per 100 parts of chlorinated rubber of at least oneplasticizer of the formula:

wherein R is alkylene selected from the group consisting of CH; $152;iand H CH3 Ar and Ar;; are each selected from the group consisting ofphenyl and lower alkylphenyl; and Ar is selected from the groupconsisting of phenylene and lower alkylphenylene; the total number ofalkyl groups in each Ar Ar 3. A painting composition according to Claim1 wherein the plasticizer comprises a compound in which R is Ar and Arare each phenyl; and Ar is meta cresylene. 4. A painting compositionaccording to claim 1 wherein the plasticizer comprises a mixture ofcompounds in 7 Ar and Ar are each phenyl; and Ar is meta-dimethylphenylene; (D) R is A1; is phenyl; Ar; is phenylene; and Ar;; ismeta-dimethyl phenyl; (E) R is Ar and Ar is phenyl; and Ar is ethylphenylene; (F) R is E (|'j H Ar is phenyl; Ar is phenylene; and Ar isethyl phenyl. 5. A painting composition according to claim 1 wherein theplasticizer comprises a mixture consisting of compounds in which: (A) Ris CH; Ar and Ar are each phenyl; and Ar is trimethyl, methyl-ethyl,iso-propyl, or n-propyl phenylene; (B) R is C JHs Ar and Ar are eachphenyl; and Ar is trimethyl, methyl-ethyl, iso-propyl or n-propylphenylene; (C) R is Ar and Ar are each methyl phenyl; and Ar istrimethyl, methyl-ethyl, iso-propyl r n-propyl phenylene; (D) R is Ar;is methyl phenyl; Al'g is methyl phenylene; and Ar is phenyl.

6. A painting composition according to claim 1 wherein the plasticizercomprises a mixture consisting of compounds in which:

(A) R is 8 Ar; and Ar are each methyl phenyl; and Ar is orthodimethylphenylene; (B) R is E ..C l H Ar and Ar;, are each methyl phenyl; and Aris metadimethyl phenylene; (C) R is t Ar and Ar;, are each methylphenyl; and Ar is ethyl phenylene; (D) R is Ar is methyl phenyl; Ar ismethyl phenylene; and Ar is ortho-dimethyl phenyl; (E) R is Ar is methylphenyl; A1' is methyl phenylene; and An, is meta-dimethyl phenyl; (F) Ris Ar is methyl phenyl; Ar is methyl phenylene; and Ar is ethyl phenyl.

References Cited UNITED STATES PATENTS 3,069,478 12/1962 McLaughlin260668 C 2,402,189 6/1946 Soday 260-735 2,772,172 11/1956 Carson 26O73 5US. Cl. X.R.

26033.6 UA, 668 R, 668 C, 736, 738

UNITED STATES PATENT O FFICE 5 CERTIFICATE OF CORRECTION PATENT NO.3,833,680 I DATED I September 3, 197" INVENTOR(S) Michiaki Torii l t iscertified that enor appears in the above-identified patent and that saidLetters Patent are hereby corrected as shown below:

Table 3 at Column 5, lines 53-59 should read as follows:

The product of this invention LD50 (rat, oral administration(1,2-bis-a-methylbenzyl- 10.19 g/kg l,5-dimethylbenzene) PCB LD50(meuse, oral administration) 1.8 g/kg Signed and sealed this 29th a of-April 1975;

(SEAL) Attest:

c MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officerand Trademarks

